Rubber like masses containing olefine naphthalene polymerizates



Patented June 27,. 1933 UNITED STATES PATENT OFFICE KiUB'I KEISEN'BURG,01" LEVEBK'USEN, AND WALTER BOOK, OF COLOGKE-ITULH'EII, GERMANY,ASSIGNOBS TO' I. G. FARBENINDUSTR-IE AKTIENGESELLSCHAFT, OF

FBANKFORT-ON-THE-MAIN, GERMANY, A CORPORATION OF GEBM'ANY RUBBER LIKEmassns CONTAINING OLE-FINE NAPHTHALENE roLmEaIzA'rEs moreparticularly ofa hydrocarbon of the,

probable formula capes-( horn I wherein a: means hydrogen or methyl,with b a polymerization product of an olefine naphthalene, such as alphavinylnaphthalene, homologues thereof, polyvinylnaphthalenes and thelike. The incorporating and efi'ecting of complete interpenetration ofthe butadiene hydrocarbonand olefine naphthalene polymerizate is bestperformed by mixing the difierent hydrocarbons and causingpolymerization of the mixture either by simple heating, for .example, toabout 40-80" (1.,

or in emulsion with Water and an emulsifying agent or an emulsoidcolloid, preferably while gently heating the emulsion to about 3070 C.while shaking or stirring the mixture. It will be likewise possible tointimately mix incompletely polymerized butadiene hydrocarbons withincompletely polymerized olefine naphthalenes, which polyimerizedproducts should still possess a somewhat viscous character, bymechanical means and causingfurther polymerization of the mixtures thusobtained according to one of the processes above mentioned with orwithout the addition of further butadienc hydrocarbon and/or olefinenaphthalene hydrocarbon. Obviously our, mixed rubberlike masses can alsobe obtained by at first partially polymerizing a butadiene hydrocarbon,then adding an olefine naphthalene hydrocarbon and further polymerizingaccording to one of the methods described above or vice versa. It may bementioned that in the claims the expression efiecting' completeinterpenetration of a heat or emulsion 'polymerizate derived from acompound of the probable formula i g g wherein 2: stands for. hydrogenor nTethyl,

. f No Drawing. Application filed July 10,1980, Serial No. 467,125, andin Germany April 25, 1930.

with a heat or emulsion polymerizate of an olefine naphthalene, isintended to include all the modifications defined. above. Obviously alsosuch processes are within the scope of this expression, in whichingredients known to favorably influence the polymerization processes inquestlon, such as oxygen,

substances splitting ofif oxygen, metal oxides.

electrolytes and the like are employed.

It may further be mentioned that rubberally are obtained when employingthe olefine mixed rubber-like iasses contain between about 15-40% by wight of the olefine naphthalene polymerizate.

Instead ofthe .pure butadiene hydrocarbons or pure olefine naphthalenesthe cheaper technlcal raw products or mixtures of butadlene withisoprene and/or mixtures of different olefine 'naphthalenes or theincompletely polymerized product of the said hynaphthalene in en? anamount that the drocarbons may be employed in many caseswith goodresults.

It will also -'be advantageous in some cases to add before or duringpolymerization rather'small amounts of other diolefine hydrocarbons,such as 2.3-dimethyl-butadiene, phenyl-butadiene or the like, by whichadditions the character of the final products can be somewhat altered. I

The mixed polymerizates thus obtainable are good plastics and easilyworkable on rollers and yield vulcanizates of high technical value,especially when vulcanized after the addition of a suitable sootvariety.

It may be mentioned that the use of-olefine naphthalenes as comparedwith the use of olefine benz'enes as described in a co-pendingapplication Ser. No. 467,126 of even date has the advantage that themixed polymerizates containing olefine naphthalenes are obtained in abetter yield than those containing olefine benzenes and that the arestill more plastic and more easily wor able on rollers. Olefine benzenesand olefine naphthalenes therefore are not to be considered asequivalents in polymerization processes.

- It may further zation products obtainable from the mixed rubber-likemasses described above are generally superior in view of theirmechanical roperties to the vulcanizates obtainable rom thecorresponding butadiene or isoprene polymerizate' not containing anole,- fine naphthalene polymerizate. This is surprising inasmuch as theolefine naphthalene 'polymerizates possess a hard resin like characterand, furthermore, in view of the fact that an advantageous change inmechanicalproperties due to the presence of an olefine naphthalenepolymerizate cannot be observed it instead of a heat or emulsionpolymerizate of butadiene or isoprene a sodium polymerizate oi the samehydrocarbons is employed. 1

As mentioned above our new mixed polymerizates are very plastic andeasily workable on rollers in consequence of Which fact they very easilytake up fillers, such as soot, colloidal silicic acid, aluminium oxide,zinc oxide and the like, vulcanizing agents, such as sulfur, selenium,etc., vulcanization accelerators, plasticizing agents, dyestuffs andother ingredients usually. applied in vulcanization, processes.

By vulcanizing mixtures of our new mixed polymerizates aiter -havingincorporated therewith about 20-70% their Weight of a suitable sootvariety, "such as carbon black,

oil soot and the like, and in addition, sulfur in an amount betweenabout 0.55% by Weight of the butadiene hydrocarbon oletine naphthalenehydrocarbon polymerizate mix ture and further, if desired, otheringredients as defined above, vulcanizates are obtainable whichgenerally Will possess a tensile strength between about 180-350lag/scion"; at a stretch. between about 500-80075.

The vulcanization process may be performed by heating the vulcanizationmixture to a suitable temperature, for example, to a temperature betweenabout 100-l50 G, the time oil vulcanization obviously being de pendenton the type of vulcanization accelerator used. The following examplesillustrate our invention, Without limiting it thereto; the parts beingby volume y l Example 1.-65 parts of butediene-i 1' 3, parts ofalpha-,vinylnaphthalene, 100 parts of a 10% aqueous solution of sodiumoleate and 3 parts of 1/1 normal caustic'soda solution are emulsified ina pressure vessel and polymerized with agitation for-five days at 60 C.A cream-like paste is obtained, which can be coagulated by acidificationor by cooling; the yield of coagulate obtained amounts to about 90%. Onvulcanizing the coagulation product with the addition of lamp black bementioned that vulcaniwool tar and colophony,

relates a soft rubber like mass of very high strength and elasticity isobtained.

By employing in the above example 8 parts of 1/1 normal caustic sodasolution instead of '3 parts, the yield of the polymerization product isincreased by about 35%. The mixed rubber-like mass thus obtainableyields a vulcanization product similar to that described in the firstpart of this example, but possesses a considerably higher elongation.

Example .@.-7 5 parts of butadiene-l :3, parts ofalpha-vinylnaphthalene, 100 parts of a 10% aqueous solution of sodiumoleate and 3 parts of 1/1 normal caustic soda solution are emulsifiedand polymerized as described in Example 1. After coagulation of thelatex-like mass, :1 strong plastic polymerization product is obtained ina yield of about 94% and the vulcanization product of the latter,besides possessing high strength and good elasticity, is especiallydistinguished by a good elongation.

Emample 3-68 parts of butadiene-l 3 and 20 parts of: vinylnaphthaleneare emulsitied with 80 parts of a 2% aqueous solution of thehydrochloride of the diethylaminoethoxyanilide of oleic acid and theemulsionis agitated for 4 days at C. A. latex-like paste is obtained ina substantially quanti tative yield, from which the mixed rubberlikemass can beobtained by coagulation. The mixed rubber-like masses thusobtained may be vulcanized,- for example, in the following manner:

into 100 parts by Weight of a mixture of this polymerizate with parts byWeight of gas-black are rolled in 15 parts by Weight of zinc-oxide, 4parts by weight of a mixture obtained by melting together equal parts ofstearic acid, 15 parts by Weight of sulfur and 1.8 parts by Weight 0% avulcanization accelerator, the mixture is vulcanized in the usualmanner, A soft rubber-like product of a good elongation is thusobtained, possessing a tensile strength of 250-260 kg/sqem at anextensibility of 500600% and an elasticity of 47-50%.

1. The process which comprises incorpo rating Within a mixed rubber-likemass obtained by eiiecting complete interpenetration 2 parts by'weightof J ill? of a heat or emulsion polymerizate derived from a compound ofthe probable formula 1- CH2=CH(E=CH2 and about 70% by wei ht of themixed rubber-like mass employe and vulcanizing the mixture. 1

2. The process which comprises incorporating within a mixed rubber-likemass obtained by effecting complete interpenetration of a heat oremulsion polymerizate derived from a compound of the probable formulaCHFCHG=CHI i wherein m stands for hydrogen or methyl, with a heat oremulsion polymerizate derived from a vinyl naphthalene hydrocarbon inrating within a mixed l'ubben-like mass obtained by effecting completeinterpenetration of a heat or emulsion polymerizate derived from acompound of the probable formula cnz=ou p=orn wherein m stands forhydrogen or methyl, with a heat or emulsion polymerizate derived from avinyl naphthalene hydrocarbon in such a manner thatthe mixed polymerizate contains between about 15 and about by weight of the vinylnaphthalenepolymerizate, sulfur .in an amount between about 0.5 andabout 5% by weight of the mixed polymerizate employed and carbon blackin an amount between about 20 and about 7 0% by weight of the mixedpolymer? zate employed and vulcanizing the mixture.

4. The process which comprises incorporating within a mixed rubber-likemass obtained by effecting complete interpenetration of a heat oremulsion polymerizate derived from a compound of the probable formula:

CH1=CH(|J=CH:

wherein a: means hydrogen or methyl, with a heat or emulsionpolymerizate derived from alpha-vinyl naphthalene, in such a manner thatthe mixed polymerizate contains below about by weight of thealpha-vinylnaphthalene polymerizate, sulfur in an 7 amount between about0.5 and about'5% by weight of the mixed polymerizate employed and carbonblack in an amount between about 20 and about by weight of'the mixedpolymerizate employed and vulcanizing the mixture.

5. The process which comprises incorporating within a mixed rubber-likemass obtained by efi'ecting complete interpenetration of a heat oremulsion polymerizate derived from a compound of the probable formulacm=on-pcin i 2: wherein a: stands for hydrogen or methyl,

with a heat or emulsion polymerizate derived from alpha-vinylnaphthalene in such a manner that the mixed polymerizate containsbetween about 15 and about 40% by weight of the alpha-vinyl-napthalenepoly.- merizate, sulfur in an amount between about i 0.5 and about 5% byweight of the mixed polymerizate employed and carbon black in an amountbetween about QOandabout 70% b weight of the mixed polymerizateemployed, and vulcanizing the mixture.

6 The vulcanizates being obtainable in accordance with the process orclaim 1, said vulcanizates possessing high grade technical propertiesapproaching or, in many cases, even surmounting those of natural rubberpolymerizates.

7. The new vulcaniizates being obtainable in accordance with tlieprocess of claim 2, said vulcanizates generally possessing a tensilestrength between about 180350 kg/sqcm at a stretch between about500800%.

8. The new vulcanizates being obtainable in accordance with the processof claim 3, said vulcanizates generally possessing a tenat a stretchbetween about 500800%.

9. The new vulcanizates being obtainable in accordance with the processof claim 4, said vulcanizates generally possessing a tensile strengthbetween about 180350 kg/sqcm at a-stretch between about 500800%.

10. The new vulcanizates being obtainable in accordance with the processof claim 5, said vulcanizates generally possessing a tensile strengthbetween about 180-350 kg/sqcm at a stretch between about 50O8O0%.

In testimony whereof, we aflix our signatiires. v KURT MEISENBURG.WALTER BOOK.

IOI

sile strength between about 180-350 kg/sqcm

